Porous spherical cellulose acetate particles

ABSTRACT

Cellulose acetate is formed into porous, spherical particles, having an acetylation degree of 49 to 60%, a particle diameter of 0.05 to 10 mm, a sphericity of 0.7 or larger, a pore volume of 0.4 cc/g or larger and a collapsing strength of 9 kg or higher.

The invention relates to particles of cellulose acetate and then aprocess for preparing the same. Cellulose acetate which the inventionespecially concerns has a combined acetic acid, or an acetylationdegree, of 49 to 60%, which corresponds to an esterification degree of2.0 to 2.8.

Cellulose acetate is known to have moldability and solubility in commonorganic solvents such as acetone, acetic acid and ethyl acetate. Forthis reason it has been used in the form of chips, flakes, powder,fiber, film or moulded articles.

While moldings of cellulose acetate are excellent in propertiesincluding transparency, dyeability, touch, impact strength, etc., thismaterial itself exhibits properties such as adsorptivity, liquidretentivity, and easy wettability of its surface. Therefore, ifparticles that are both porous and spherical can be obtained from it,these particles will be useful as enzyme carriers, chromatographicpackings, slow-releasing adsorbents for perfuming agents, deodorants,medicines or agricultural chemicals, and ion exchangers. The reason whyspherical particles are advantageous is that they have good fluidity ascompared with particles of other shapes. For example, sphericalparticles carrying an enzyme give a good efficiency of contact with areaction solution when they are used in a packed bed, a fluidized bed,or an agitation tank. In this case, it is desirable that disintegrationor deformation of particles does not occur even when the height of thepacked bed is increased or when a pressure or an impact of the blade ofthe agitation tank is exerted on the particles. The disintegration ordeformation of the particles in a packed bed results in the formation ofunevenly dense portions and causes an uneven flow of a reaction solutionand a lowered reaction efficiency. Therefore, the particles must bethose which are tough enough to withstand compression or impact.

On the other hand, the particles must have a large pore volume becausethe amount of an enzyme or a drug fixed or a adsorbed thereon isproportional to the pore volume within the particles. Particles of alarge pore volume necessarily have a small specific gravity. In general,the requirement that particles should have a small specific gravity ordensity is contradictory to the requirement that they should havesufficient toughness and, therefore, none of the prior art has succeededin meeting both of these requirements.

As a result of extensive studies, the inventors of the present inventionhave succeeded in producing porous spherical particles having a goodsphericity, a toughness, and a large pore volume by using celluloseacetate as a starting material.

According to the invention, cellulose acetate is formed into porous,spherical particles, having an acetylation degree of 49 to 60%, aparticle diameter of 0.05 to 10 mm, a sphericity of 0.7 or larger, apore volume of 0.4 cc/g or larger and a collapsing strength of 9 kg orhigher.

In a preferable embodiment, a sphericity is 0.8 or greater, a porevolume is 0.65 cc/g or greater and a degree of esterification is 2.0 to2.8.

In addition, the invention includes an improvement that the surface ofthe above defined particles has been saponified. This surface-saponifiedparticles have the surface portion consisting essentially of celluloseand the core portion consisting essentially of cellulose acetate, havingan acetylation degree of 48 to 59%, a particle diameter of 0.05 to 10mm, a sphericity of 0.7 or greater, a pore volume of 0.4 cc/g or greaterand a collapsing strength of 10 kg or higher.

In a more preferable embodiment of the surface-saponified particles, anacetylation degree of 50 to 58% and a particle diameter is 0.5 to 10 mm.

The process for producing spherical particles according to the presentinvention is the so-called "precipitation process". This processconsists in using a solution of a high-molecular substance as a dope;adding said dope to a bath comprising a medium in which thehigh-molecular substance is not soluble but the solvent of said solutionis soluble, that is, a coagulation bath; and applying thereto a shearingforce to form particles while precipitating the high-molecular substanceby solvent removal.

In the present invention, acetic acid/water mixtures are used as thesolvent for a cellulose acetate solution, that is, a dope, and themedium for a coagulation bath. The solvent for the dope has acomposition of an acetic acid to water ratio of 80/20 to 90/10 (byweight; the same applies hereinafter), and the medium for thecoagulation bath has a composition of an acetic acid to water ratio of30/70 to 42/58.

The dope is prepared by dissolving a cellulose acetate of a degree ofesterification of 2.0 to 2.8 in the above solvent for a dope so that theconcentration of the cellulose acetate may be 25±7% (by weight; the sameapplies hereinafter), preferably about 25%. It is preferable that theviscosity of the dope is about 2,000 poises at 40° C. A supply pipeleads from a dope tank to a coagulation bath, and a nozzle on one end ofthe supply pipe is submerged in the coagulation bath. The coagulationbath is provided with an agitator having blades thereon. Each of theblades has a cutting edge on the front side to pass near the holes ofthe nozzle and cut a rod-like continuous body of the dope which isextruded from the holes of the nozzle and is coagulating. The cut finepieces form spherical particles while they are precipitating andcoagulating.

Since the acetic acid concentration of the acetic acid/water solutionbrought in by the dope during continued performance of the precipitationand coagulation is higher than the initial acetic acid concentration ofthe coagulation bath, it is necessary to maintain the acetic acid towater ratio of the coagulation bath constant by adding such an amount ofwater as to counterbalance the acetic acid brought in. This addition ofwater makes it possible to keep the concentration gradient ofparticle/medium constant to thereby afford uniform particlescontinuously.

The size of particles obtained by this process depends on a nozzle holediameter, a feed rate of a dope, an agitator speed, etc., and thesphericity is improved when the feed rate and the agitator speed are setsuch that the cut length of the rotor may be nearly equal to the nozzlehole diameter. Particles having a particle diameter in the range of 0.05to 10 mm are practical. Those having a particle diameter of less than0.05 mm show a poor efficiency of production, while those having aparticle diameter exceeding 10 mm can difficultly acquire an excellentsphericity or a pore volume.

In the process of the present invention, it is also possible to use anaged dope formed in the step of producing a cellulose acetate having adegree of esterification of 2.0 to 2.8 directly as the dope for theprecipitation step. Namely, while this cellulose is one which isobtained by saponifying and aging cellulose triacetate by treatment withan acetic acid/water solvent, the reaction solution at the time ofcompletion of the aging is called aged dope, because it is in a state inwhich a cellulose acetate of a degree of esterification of 2.0 to 2.8 isdissolved in a highly concentrated aqueous acetic acid solution, and hasa viscosity of as high as about 1,000 to 3,000 poises. The separatingand recovering step of cellulose acetate from the aged dope is theso-called "precipitation step". It is to be noted that the aged dopeusually contains an inorganic salt, e.g., magnesium sulfate, which is aproduct of neutralization of a catalyst (usually, sulfuric acid) used inthe acetylation reaction. If such a water-soluble salt is present in alarge amount, the size of the internal pores will tend to increase inthe precipitation step, thus reducing the pore volume. Therefore, it ispreferable that the salt content of the aged dope when it is sent to theprecipitation step is 1.5% or below. The salt content depends on theconditions of the acetylation step, that is, on the amount of a catalystused, so that it is necessary to choose conditions including a smalleramount of catalyst used. Such a process for the acetylation underconditions of a smaller amount of a catalyst is described, for example,in Japanese Patent Laid-Open No. 59801/1981.

The particles according to the process of the present invention arethought to be formed in such a manner that a tough shell portion isformed during a relatively early period of the precipitation step andthen a thick aqueous acetic acid solution held within the particles isreplaced with a relatively thin aqueous acetic acid solution in thecoagulation bath, during which time the internal pores are formed.Namely, it may be presumed that the tough shell is formed on aninterface of a relatively large concentration gradient and, thereafter,the replacement of the solvents at a relatively smaller concentrationdifference proceeds within the particles, and passages left after thehighly concentrated aqueous acetic acid solution has passed frominternal pores.

Although, as can be seen from the above, the structure of a particle isestablished almost completely in the precipitation step, the particlesstill contain a large amount of acetic acid within them. These particlesare centrifugally separated from the solution, subjected to a washingtreatment in a water bath and then dried. The acetic acid remainingwithin the particles is replaced with water in the washing step, so thatthe structure of a particle is affected somewhat by the conditions ofthe washing step. Namely, it is preferable that the washing is carriedout with water of 40° to 90° C. Particles of a larger pore volume can beobtained if the above treatment is carried out at a higher temperature.

The spherical particles of the present invention are extremely tough andhave a large pore volume, so that they are highly suited for use inpackings, carriers, adsorbents, etc. Further, because of the toughnessof their shells, the particles can be used also in the production ofsintered bodies.

When the particles must have surfaces which are more hydrophilic thanthose of the cellulose acetate, or when the particles are used incontact with a medium which dissolves, swells, or plasticizes thecellulose acetate, they are used in the form of regenerated celluloseparticles which can be obtained by saponifying the cellulose acetateparticles with an alkali. This saponification may be effected to such anextent that only the surface are saponified or that the particles arecompletely saponified. It is also possible to obtain hollow particles ofregenerated cellulose by saponifying only the surface and treating theparticles with a solvent which dissolves cellulose acetate.

The surface-saponified particles of the invention is prepared by soakingthe porous, spherical particles of cellulose acetate as disclosed abovewith an aqueous solution of sodium hydroxide having a concentration of0.2 to 2 wt. % for 1 to 6 minutes at a ratio of liquid to solid in therange between 3 and 10.

The comparison between the particles before the surface saponificationof the present invention and those after the surface saponification ofthe present invention has revealed that the particle diameter and thesphericity are somewhat reduced and the pore volume is also reduced, butthat the collapsing strength is somewhat increased in some cases, ordecreased in other cases. It was also found that a content of combinedacetic acid representative of the composition was kept at 95% or above,suggesting that only a small portion of each particle was saponified.

It is doubtless that the saponification occurs on only the very surfacesof particles in view of the fact that the surfaces of the particlesafter the saponification treatment are modified and a high content ofcombined acetic acid is maintained as mentioned above. The reason whythe saponification cannot be attained except on the surfaces, althoughthe particles before saponification are porous and have excellentimpregnatability, may be that the aqueous alkali solution which is usedin the present invention imparts moderate swellability to the surfacesof the particles to be treated, and this prevents the alkali frominfiltrating into the insides of the particles. It is presumed that thissurface-swollen layer is reconverted into a layer which is porous yetdense, when the treated particles are washed with water and dried.

The surface-saponified porous spherical cellulose acetate particles ofthe present invention have the same applications as those of the porousspherical cellulose acetate particles before the surface saponification,and have a particularly excellent effect of impregnation and release ofpolar substances.

Although the present invention relates to surface-saponified porousspherical cellulose acetate particles and to a process for producing thesame, it is also possible to produce surface-saponified porous sphericalparticles of lower fatty acid cellulose esters, such as cellulosepropionate and cellulose butyrate, as substitutes for cellulose acetate,by a similar and to use these in similar applications.

The present invention will be described with reference to an example,but it should be noted that the present invention is by no means limitedthereto.

EXAMPLE 1

A ripening dope containing a cellulose diacetate concentration of 25%, amagnesium sulfate concentration of 0.9% and a viscosity at 40° C. of2,100 poises was added to a coagulation bath of a composition of anacetic acid to water ratio of 40/60 to effect precipitation andgranulation. The apparatus was operated by using a nozzle diameter of 3mm, a revolution speed of a three-blade agitator of 1,000 rpm, and acoagulation bath temperature of 40° C. to obtain spherical precipitatedparticles. The particles were centrifugally separated, washed with waterof 60° C., and dried.

The physical properties of the particles were measured according to thefollowing methods.

Sphericity

20 particles were taken up at random and the largest and smallestdiameters of each particle were measured with a micrometer. Thesphericity was determined according to the following equation. ##EQU1##

Pore Volume

A mercury porosimeter (a product of Carlo Erba) was used. The volume ofmercury intruded into the pores at a pressure in the range of 0 to 1,000(kg/cm² G) corresponded to a volume of pores in the range of 75 to75,000 (Å). The pore volume is represented in terms of cc per one gramof the sample.

Collapsing strength

A Monsanto tablet hardness tester (a product of Oiwa Medical MachineManufacturing Co., Ltd.) was used. An average of the measured values of10 particles was calculated.

The determined values of the produced spherical particles are asfollows:

    ______________________________________                                        sphere diameter  3.5        4.0 mm                                            sphericity       0.82                                                         pore volume      0.81       cc/g                                              collapsing strength                                                                            11.1       kg.                                               ______________________________________                                    

Content of combined acetic acid

About 5 g of a powdered sample was dried in a dryer at 100° to 105° C.for 2 hours, and weighed accurately. 50 cc of purified acetone was addedto this sample and the mixture was dissolved completely. 50 cc of a 0.2Naqueous NaOH solution and 50 cc of a 0.2N aqueous HCl solution wereadded thereto in sequence. The resulting solution was titrated with a0.2N aqueous NaOH solution by using phenolphthalein as an indicator. Thedegree of acetylation was calculated according to the followingequation: ##EQU2## wherein A: volume (cc) of 0.2N aqueous NaOH solution

B: volume (cc) of 0.2N aqueous NaOH solution added in a blank test

F: factor of 0.2N aqueous NaOH solution.

In the invention, a combined acetic acid or a content of combined aceticacid which is determined in the above shown manner is called also as anacetylation degree. This may be calculated to an esterification degree.

EXAMPLE 2

1,000 g of porous spherical particles comprising cellulose acetate of adegree of acetylation of 54.5% (a product of Daicel Chemical Industries,Ltd.), and having an average particle diameter of 3.6 mm, a sphericityof 0.87, a collapsing strength of 15 kg, and a pore volume of 0.68 cc/gwere immersed in 500 cc of a 1% aqueous solution of sodium hydroxide atthe room temperature for 3 minutes. After centrifugally separating thesolution, the particles were washed with warm water of 40° C. until thewashing became neutral, and then dried in a dryer at 100° to 110° C. for3 hours to obtain surface-saponified porous spherical particles. Theseparticles had an average degree of acetylation of 53.4%, an averageparticle diameter of 3.2 mm, a sphericity of 0.82, a pore volume of 0.43cc/g, and a collapsing strength of 17 kg.

EXAMPLE 3

100 g of porous spherical particles comprising cellulose acetate of adegree of acetylation of 55.2% (a product of Daicel Chemical Industries,Ltd.), and having an average particle diameter of 5.3 mm, a sphericityof 0.90, a collapsing strength of 14 kg, and a pore volume of 0.75 cc/gwere immersed in 500 cc of a 0.5% aqueous solution of sodium hydroxideand treated in the same manner as that in Example 2 to obtainsurface-saponified porous spherical particles. These particles had anaverage content of combined acetic acid of 54.5%, an average particlediameter of 5.1 mm, a sphericity of 0.85, a pore volume of 0.51 cc/g,and a collapsing strength of 15 kg.

APPLICATION EXAMPLE

2 g of bergamot oil (linalyl acetate content of 40%) was added to 10 gof the surface-saponified spherical particles obtained in Example 2 andthe mixture was agitated. After about 10 minutes, the liquid wascompletely impregnated, and the surfaces of the particles became dry andnonsticky. Separately, the spherical particles before surfacesaponification used in Example 2 were impregnated with a perfume by asimilar treatment. The surfaces of the particles were sticky and tendedto stick to each other.

On the contrary, when the surface-saponified spherical particles whichwere obtained in Example 2 and impregnated with a perfume were stored at80° C., their surfaces did not become sticky.

The evaporation rate of the perfume in an open air at a room temperaturewas determined. 10 days were necessary for 50% evaporation, and 45 dayswere necessary for 90% evaporation. This suggested an excellent effectof slow releasing.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:
 1. Porous, sphericalparticles of cellulose acetate, which consist essentially of celluloseacetate havingan acetylation degree of 49 to 60%, a degree ofesterification of from 2.0 to 2.8, a particle diameter of 0.05 to 10 mm,a sphericity of 0.8 or larger, a pore volume of 0.65 cc/g or larger anda collapsing strength of 9 kg or higher.
 2. Porous, spherical particlesas claimed in claim 1, the surface of which has been saponified.
 3. Aprocess for producing porous spherical cellulose acetate particles,which comprises feeding a dope comprising a solution formed bydissolving a cellulose acetate of a degree of esterification of 2.0 to2.8 in an acetic acid/water (80/20 to 90/10, by weight) solvent so thatthe concentration of the cellulose acetate may be 25±7 wt. %; feedingsaid dope through a supply pipe to a coagulation bath comprising anacetic acid/water (30/70 to 42/58, by weight) solvent and having atemperature of 40°±5° C.; operating an agitator having a rotor passingnear a discharge port on the end of said supply pipe; effectingprecipitation and granulation while adding water so that the acetic acidto water ratio of the coagulation bath may be maintained at asubstantially constant value during said operation; centrifugallyseparating precipitated particles from the solution; washing theseparticles with water of 40° to 90° C.; and drying the particles.
 4. Aprocess for producing porous spherical cellulose acetate particles,which comprises: providing a dope comprising a solution formed bydissolving (1) cellulose acetate having a degree of esterification offrom 2.0 to 2.8, in (2) a solvent comprising a first mixture of aceticacid and water in which the weight ratio of acetic acid/water is from80/20 to 90/10, said dope containing from 18 to 32 wt. % of saidcellulose acetate; providing a coagulation bath comprising a secondmixture of acetic acid and water in which the weight ratio of aceticacid/water is in the range of from 30/70 to 42/58; feeding a stream ofsaid dope through a supply pipe into said coagulation bath having atemperature of 35° to 45° C., simultaneously operating an agitatorhaving a rotor that passes near the discharge end of said supply pipe tobreak up said stream into droplets, said droplets precipitating in theform of spherical cellulose acetate particles in said coagulation bath,and adding water to said coagulation bath to maintain the weight ratioof acetic acid/water in said coagulation bath in said range of from30/70 to 42/58 while said dope is being fed into said coagulation bath;then separating said precipitated spherical particles from saidcoagulation bath; washing said particles with water having a temperatureof 40° to 90° C.; and then drying said particles.
 5. A process asclaimed in claim 4 in which said dope contains about 25 wt. % of saidcellulose acetate.
 6. A process as claimed in claim 4 in which saidstream of dope is extruded through a nozzle in the form of a rod-likecontinuous body into said coagulation bath so as to begin coagulatingtherein and said rotor comprises blade means for cutting said rod-likecontinuous body into fine pieces which form into spherical particles asthey continue precipitating in said coagulation bath.
 7. A process asclaimed in claim 4 including the additional step of saponifying thesurfaces of said particles after the step of drying said particles.
 8. Aprocess as claimed in claim 4 in which, after the step of drying saidparticles, said particles are immersed in an aqueous solution of sodiumhydroxide having a concentration of 0.2 to 2 wt. %, for 1 to 6 minutes,wherein the ratio of said aqueous solution to said particles is between3 and 10, whereby to saponify the surfaces of said particles, and thenrecovering the saponified particles.
 9. Saponifield porous sphericalparticles having a cellulose acetate core and a cellulose shell, saidparticles having been prepared by the process of claim 8 and havinganacetylation degree of 48 to 59%, a particle diameter of 0.05 to 10 mm, asphericity of 0.7 or larger, a pore volume of 0.4 cc/g or larger and acollapsing strength of 10 kg or higher.
 10. A process as claimed inclaim 4 in which said dope is an aged dope prepared by acetylatingcellulose to form cellulose triacetate and then saponifying and agingsaid cellulose triacetate with a mixture of acetic acid and water untilthere is obtained a dope containing cellulose acetate having a degree ofesterification of 2.0 to 2.8, said aged dope containing 1.5 wt. % orless of an inorganic salt.
 11. Porous spherical cellulose acetateparticles prepared by the process of claim 4 and havingan acetylationdegree of 49 to 60%, a degree of esterification of from 2.0 to 2.8, aparticle diameter of 0.05 to 10 mm, a sphericity of 0.8 or larger, apore volume of 0.65 cc/g or larger and a collapsing strength of 9 kg orhigher.